Detergent compositions having suds suppressing properties

ABSTRACT

A detergent composition formulated with conventional detersive surfactants, optional builders, detergent adjuncts and a suds suppressor, wherein said suds suppressor is an amino acid of formula (I), or its alkali metal, alkaline earth metal salt or mixtures thereof, wherein R 1  is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R 2  is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R 5  is H or an alkyl aryl, or alkaryl group containing from 1 to 10 carbon atoms. The invention also relates to a detergent composition comprising a mixture of amidoacid and amidoperacid suds suppressors and to an aqueous wash liquor containing a detersive surfactant comprising a C 10  -C 20  alkyl sulphate, optionally together with builders and detergent adjuncts and a suds suppressor compound wherein said suds suppressor is formed from a suds suppressor precursor. ##STR1##

FIELD OF THE INVENTION

The present invention relates to detergent compositions having sudssuppressing properties. More particularly, the present invention relatesto new suds suppressor compounds.

BACKGROUND OF THE INVENTION

Detergent compositions containing high levels of surfactants are knownin the art. Surfactants such as anionic, nonionic or cationic arerequired to aid grease removal and maintain soil suspension fromfabrics. More particularly, high levels of anionic surfactants aredesirable to provide whiteness maintenance. However, a problemencountered with the use of some high levels of surfactants, especiallyhigh foaming anionic surfactants, is the propensity of the surfactant togive high levels of sudsing; this problem being particularly more acuteat high temperature.

Traditionally, the suppression of suds has been enabled by the use ofhigh level of suds suppressor such as silicones, fatty acids and twinchain alcohols. However a problem encountered by such use is theirexpensive cost for few detergency benefits.

Peracid precursors are also known for providing more effectivebleaching. Particularly effective are the hydrophobic bleach precursorsuch as Nonanoyl Oxy Benzene Sulphonate (NOBS), which generates a fattyacid by-product in the wash liquor. However, this is ineffective atcontrolling suds in high temperatures wash conditions.

Further hydrophobic bleach precursors known in the art are described inU.S. Ser. No. 08/064,563 and EP 0170386.

U.S. Ser. No. 08/064,563 teaches an amidoperoxy compound and itsprecursors such as (6-octanamidocaproyl) oxybenzenesulphonate,(6-nonamidocaproyl) oxybenzene sulphonate, (6-decanamidocaproyl)oxybenzene sulphonate and mixtures thereof compatible with enzyme whichhas a bleach cleaning and enzyme cleaning performance. It discloses adetergent composition with nil-LAS surfactant, and teaches that theamidoperoxy compound can be formulated with hydrophilic activators suchas TAED. EP 0170386 teaches amidoperoxy compound and their precursors ina peroxygen bleaching composition which provide effective bleaching oftextiles over a wide range of temperatures.

It has now been found that amidoperoxy compounds and their precursorssuch as described in U.S. Ser. No. 08/064,563 and EP 0170386 givesfurther enhanced suds suppressing properties.

Furthermore, it has also been found that amidoacid compounds have sudssuppressing properties.

It is an object of the invention to provide a detergent compositioncomprising new suds suppressor compounds selected from amidoacid andmixtures of amidoacid and amidoperacid. It is further object of theinvention to provide an aqueous wash liquor containing a detersivesurfactant comprising a C₁₀ -C₂₀ alkyl sulphate, optionally togetherwith builders, detergent adjuncts and a suds suppressor wherein saidsuds suppressor is formed from a suds suppressor precursor.

SUMMARY OF THE INVENTION

The present invention encompasses a detergent composition formulatedwith conventional detersive surfactants, optional builders, detergentadjuncts and a suds suppressor, wherein said suds suppressor is anamidoacid of formula ##STR2## or its alkali metal, alkaline earth metalsalts or mixture thereof, wherein R₁ is an alkyl, aryl or alkaryl groupcontaining from 1 to 14 carbon atoms, R₂ is an alkylene, arylene oralkarylene group containing from 1 to 14 carbon atoms, R₅ is H or analkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION

The present invention contemplates detergent compositions having sudssuppressing properties.

An essential component useful for the purpose of the invention is a sudssuppressor compound in a detergent composition formulated withconventional detersive surfactants, optional builders, detergentadjuncts, wherein said suds suppressor is selected from amidoacid andmixtures of amidoacid and amidoperacid.

Levels of said surfactants in the detergent composition will typicallybe from 1% to 80% by weight of the detergent composition and levels ofsaid suds suppressor from 0.025% to 20% by weight of the detergentcomposition.

The described compounds, i.e. amidoacid and mixture of amidoacid andamidoperacid, exhibit excellent suds suppressing properties and may beused as a `detergent active` suds suppressor or as a co-suds suppressoragent.

By `detergent active`, it is meant that further to its suds suppressingactivity, the amidoacid or the mixture of amidoacid and amidoperacidgives also a bleaching activity with or without a bleaching agent. Whenused as a co-suds suppressor agent, the development encompasses twoadvantages:

Firstly, it enhances the suds suppressing properties of the detergentcomposition.

Secondly, it allows the use of lower than conventional levels ofexpensive suds suppressors such as silicone, fatty acid, twin-chainalcohols; thus reducing the cost of the product.

Additionally, the suds suppressing properties of this development areretained in the presence of organic peroxyacid bleaches derived frommixtures of perhydrates and precursors which contain one or more N-acylor O-acyl group such as TAED, NOBS, acyl lactam and cationic precursors,or preformed peracids such as amido peracids or diperacids.

The presence of such peroxyacid bleaches permits the use of a widestrange of stains bleaching.

Furthermore, the amidoacid and the mixture of amidoacid and amidoperacidshow a good suds suppressing activity with surfactants selected fromanionic, cationic, nonionic ampholytic, amphoteric and zwitterionicsurfactants and mixtures thereof. Especially preferred surfactants arethose selected from anionic, nonionic, cationic surfactants and mixturesthereof.

Most preferred surfactants for an enhanced reduction of suds formed fromsurfactants are nil-LAS surfactants.

A main component useful for providing the suds suppressing properties isan amidoacid of formula ##STR3## or its alkali metal, alkaline earthmetal salts or mixture thereof, wherein R₁ is an alkyl, aryl or alkarylgroup containing from 1 to 14 carbon atoms, R₂ is an alkylene, aryleneor alkarylene group containing from 1 to 14 carbon atoms, R₅ is H or analkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms.

Another suds suppressor component useful for the present invention is amixture of amidoacid as described above and amidoperacid of formula##STR4## or its alkali metal, alkaline earth metal salts or mixturethereof, wherein R₁ is an alkyl, aryl or alkaryl group containing from 1to 14 carbon atoms, R₂ is an alkylene, arylene or alkarylene groupcontaining from 1 to 14 carbon atoms, R₅ is H or an alkyl, aryl, oralkaryl group containing from 1 to 10 carbon atoms.

Preferred suds suppressors such as described herein before are thosewherein R₁ is an alkyl group containing from 6 to 12 carbon atoms, R₂contains from 1 to 8 carbon atoms, and R₅ is H or methyl. Particularlypreferred suds suppressors are those of the above general formulaswherein R₁ is an alkyl group containing from 7 to 10 carbon atoms and R₂contains from 4 to 5 carbon atoms.

Level of said suds suppressor in the detergent composition are normallyadded at a level of from 0.025% to 20%, preferably from 0.05% to 15%,more preferably from 0.06% to 12% and most preferably from 0.06% to 7%by weight of the composition.

The detergent compositions in which said suds suppressors can be usedinclude compositions which are to be used for cleaning substrates, suchas fabrics, fibers, hard surfaces, skin, etc.; for example hard surfacecleaning compositions (with or without abrasives), laundry detergentcompositions, automatic and non-automatic dishwashing compositions.

Suds suppressor precursors

Another aspect of the present invention comprises an aqueous wash liquorcontaining a detersive surfactant comprising a C₁₀ -C₂₀ alkyl sulphate,optionally together with builders, detergent adjuncts and a sudssuppressor compound wherein said suds suppressor is formed from a sudssuppressor precursor of formula ##STR5## or mixtures thereof, wherein R₁is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms,R₂ is an alkylene, arylene or alkarylene group containing from 1 to 14carbon atoms, R₅ is H or an alkyl, aryl, or alkaryl group containingfrom 1 to 10 carbon atoms, and L is a leaving group.

L can be essentially any suitable leaving group. A leaving group is anygroup that is displaced from the suds suppressor precursor as aconsequence of the nucleophilic attack on the suds suppressor precursorby the perhydroxide anion. This, the perhydrolysis reaction, results inthe formation of the percarboxylic acid suds suppressor. A competingreaction can also occurs which is the hydrolysis reaction. Thishydrolysis reaction results in the formation of the carboxylic acid sudssuppressor. In absence of the perhydroxide anion, the nucleophilicattack is provided by the hydroxide anion which provide as for thecompeting reaction cited above an hydrolysis reaction. This results inthe formation of the carboxylic acid suds suppressor.

Generally, for a group to be a suitable leaving group it must exert anelectron attracting effect. It should also form a stable entity so thatthe rate of the back reaction is negligible. This facilitates thenucleophilic attack by the perhydroxide anion or the hydroxide anion.

The L group must be sufficiently reactive for the reaction to occurwithin the optimum time frame (e.g., a wash cycle). However, if L is tooreactive, this precursor will be difficult to stabilise in detergentcomposition. These characteristics are generally paralleled by the pKaof the conjugate acid of the leaving group, although exceptions to thisconvention are known. Ordinarily, leaving groups that exhibit suchbehaviour are those in which their conjugate acid has a pKa in the rangeof from 4 to 13, preferably from 6 to 11 and most preferably from 8 to11.

Preferred suds suppressor precursors are those of the above generalformula wherein R₁, R₂ and R₅ are as defined for the suds suppressor(amidoacid and amidoperacid) and L is selected from ##STR6## andmixtures thereof, wherein R₁ is an alkyl, aryl or alkaryl groupcontaining from 1 to 14 carbon atoms, R₃ is an alkyl chain containingfrom 1 to 8 carbon atoms, R₄ is H or R₃, and Y is H or a solubilisinggroup.

The preferred solubilising groups are --SO₃ -M+, --CO₂ -M+, --SO₄ -M+,--N⁺ (R₃)₄ X⁻ and O<--N(R₃)₃ and most preferably --SO₃ ⁻ M⁺ and --CO₂ ⁻M⁺ wherein R₃ is an alkyl chain containing from 1 to 4 carbon atoms, Mis a cation which provides solubility to the suds suppressor precursorand X is an anion which provides solubility to the suds suppressorprecursor.

Preferably, M is an alkali metal, ammonium or substituted ammoniumcation, with sodium and potassium being most preferred, and X is ahalide, hydroxide, methylsulphate or acetate anion. It should be notedthat suds suppressor precursors with a leaving group that does notcontain a solubilising group should be well dispersed in the detergentcomposition in order to assist in their dissolution.

Preferred suds suppressor precursors are those of the above generalformula wherein L is selected from ##STR7## wherein R3 is as definedabove and Y is --SO₃ ⁻ M⁺ or --CO₂ ⁻ M⁺ wherein M is as defined above.Preferably, L has the general formula: ##STR8##

The suds suppressor precursors defined herein before will comprise atleast 0.1%, preferably from 0.1% to 50%, more preferably from 0.2% to30%, most preferably from 0.5% to 25%, by weight of the detergentcomposition.

Another embodiment of the present invention is the addition to thedetergent composition of the invention of other suds suppressor agentsand/ or detersive surfactants.

When the detergent composition of the present invention is used withadditional suds suppressors such as `silicone` and anionic surfactants,both described herein after; the ratio of said anionic surfactant tosaid silicone is preferably from at least 10 to 1, more preferably fromat least 15 to 1.

Furthermore, if the anionic surfactant is alkyl sulphate, the preferredratio of said alkyl sulphate to said silicone is from at least 20 to 1.

Additional suds suppressors

A wide variety of materials, well known to those skilled in the art, maybe used as additional or co-suds suppressors. See, for example, KirkOthmer Encyclopaedia of Chemical Technology, Third Edition, Volume 7,pages 430-447 (John Wiley & Sons, Inc., 1979). One category of sudssuppressor of particular interest encompasses monocarboxylic fatty acidand soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep. 27,1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereofused as suds suppressor typically have hydrocarbyl chains of 10 to 24carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts includethe alkali metal salts such as sodium, potassium, and lithium salts, andammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetraalkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range of-40° C. and 50° C., and a minimum boiling point not less than 110° C.(atmospheric pressure). It is also known to utilise waxy hydrocarbons,preferably having a melting point below 100° C. The hydrocarbonsconstitute a preferred category of suds suppressor for detergentcompositions. Hydrocarbon suds suppressors are described, for example,in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al. Thehydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from 12 to 70carbon atoms. The term "paraffin," as used in this suds suppressordiscussion, is intended to include mixtures of true paraffins and cyclichydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to1,500 cs. at 25° C.;

(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resincomposed of (CH₃)₃ SiO_(1/2) units of SiO₂ units in a ratio of from(CH3)3 SiO_(1/2) units and to SiO2 units of from 0.6:1 to 1.2:1; and

(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solidsilica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from 0.001 to1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight% of said silicone suds suppressor, which comprises (1) a nonaqueousemulsion of a primary antifoam agent which is a mixture of (a) apolyorganosiloxane, (b) a resinous siloxane or a siliconeresin-producing silicone compound, (c) a finely divided filler material,and (d) a catalyst to promote the reaction of mixture components (a),(b) and (c), to form silanolates; (2) at least one nonionic siliconesurfactant; and (3) polyethylene glycol or a copolymer ofpolyethylene-polypropylene glycol having a solubility in water at roomtemperature of more than 2 weight %; and without polypropylene glycol.Similar amounts can be used in granular compositions, gels, etc. Seealso U.S. Pat. Nos. 4,978,471, Starch, issued Dec. 18, 1990, and4,983,316, Starch, issued Jan. 8, 1991, 5,288,431, Huber et al., issuedFeb. 22, 1994, and U.S. Pat. Nos. 4,639,489 and 4,749,740, Aizawa et alat column 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than 1,000, preferablybetween 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than 2 weight %, preferably more than 5weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than 1,000, more preferably between 100 and800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between 1:1 and 1:10, most preferablybetween 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆ -C₁₆alkyl alcohols having a C₁ -C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

Another highly preferred foam regulator system is described in WO93/17772, which system is a granular free flowing foam regulatorcontaining carrier free from surfactant. The surfactant component ispreferably a C₁₂ -C₂₂ alkyl sulphate, an alkyl polyglycoside especiallybased on glucose with a C₁₂ -C₁₈ alkyl group and/or an alkali salt of asulphonation product of a (m)ethyl ester of a C₁₂ -C₂₂ fatty acid. Thesystem is free from SiO2, the carrier is free from phosphate and iswater-soluble or -dispersible, and the paraffin wax is solid at roomtemperature and up to 100% by weight liquid at below 90° C.

By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsing producedby a solution of a detergent composition, particularly in the presenceof agitation of that solution.

An exemplary foam regulator system for use herein is granular,free-flowing foam regulator which contains:

1-a granular, surfactant-free carrier, and

2-an adsorbed uniform defoamer mixture free from siloxane polymers andemulsifying or dispersant tensides, containing

a)-70-95% by weight of a paraffin wax or mixture and

b)-30-5% of a bisamide from C₂ -C₇ diamines and C₁₂ -C₂₂ saturatedcarboxylic acids.

Another highly preferred antifoam controller is described in WO94/00547, which antifoam controller is lecithin, preferablysoya-lecithin.

The compositions herein will generally comprise from 0% to 5% ofadditional suds suppressors. When utilized as suds suppressors,monocarboxylic fatty acids, and salts therein, will be present typicallyin amounts up to 5%, by weight, of the detergent composition.Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto 2.0%, by weight, of the detergent composition, although higheramounts may be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimised and effectiveness oflower amounts for effectively controlling sudsing. Preferably from 0.01%to 1% of silicone suds suppressor is used, more preferably from 0.25% to0.5%. As used herein, these weight percentage values include any silicathat may be utilized in combination with polyorganosiloxane, as well asany adjunct materials that may be utilized. Monostearyl phosphate sudssuppressors are generally utilized in amounts ranging from 0.1% to 2%,by weight, of the composition. Hydrocarbon suds suppressors aretypically utilized in amounts ranging from 0.01% to 5.0%, althoughhigher levels can be used. The alcohol suds suppressors are typicallyused at 0.2%-3% by weight of the finished compositions.

Detersive surfactants

Nonlimiting examples of surfactants useful herein typically at levelsfrom 1% to 55%, by weight, include the conventional C₁₁ -C₁₈ alkylbenzene sulphonates ("LAS") and primary, branched-chain and random C₁₀-C₂₀ alkyl sulphates ("AS"), the C₁₀ -C₁₈ secondary (2,3) alkylsulphates of the formula CH₃ (CH₂)_(x) (CHOSO₃ ⁻ M⁺) CH₃ and CH₃(CH₂)_(y) (CHOSO₃ ⁻ M⁺) CH₂ CH₃ where x and (y+1) are integers of atleast 7, preferably at least 9, and M is a water-solubilizing cation,especially sodium, unsaturated sulphates such as oleyl sulphate, the C₁₀-C₁₈ alkyl alkoxy sulphates ("AE_(x) "; especially EO 1-7 ethoxysulphates), C₁₀ -C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers, the C₁₀ -C₁₈ alkylpolyglycosides and their corresponding sulphated polyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters.

Preferably, the detergent composition is substantially free of LASsurfactant (i.e. less than 1%, preferably less than 0.5% of LASsurfactant by weight of the composition and most preferably contains noLAS surfactant).

If desired, the conventional nonionic and amphoteric surfactants such asthe C₁₂ -C₁₈ alkyl ethoxylates ("AE") including the so-called narrowpeaked alkyl ethoxylates and C₆ -C₁₂ alkyl phenol alkoxylates(especially ethoxylates and mixed ethoxy/propoxy), C₁₂ -C₁₈ betaines andsulfobetaines ("sultaines"), C₁₀ -C₁₈ amine oxides, and the like, canalso be included in the overall compositions.

Amine oxide is a useful detersive surfactant for the purpose of theinvention as it gives a strong cleaning benefit in combination withother detersive surfactants such as Oleyl sarcosinate. Especiallypreferred, when used in combination with other surfactants, is the C14amine oxide.

The C₁₀ -C₁₈ N-alkyl polyhydroxy fatty acid amides can also be used.Typical examples include the C₁₂ -C₁₈ N-methylglucamides. See WO92/06154. Other sugar-derived surfactants include the N-alkoxypolyhydroxy fatty acid amides, such as C₁₀ -C₁₈ N-(3-methoxypropyl)glucamide. The N-propyl through N-hexyl C₁₂ -C₁₈ glucamides can be usedfor low sudsing. C₁₀ -C₂₀ conventional soaps may also be used. Mixturesof anionic and nonionic surfactants are especially useful.

Cationic surfactants can also be used in the detergent compositionsherein. Preferred cationic surfactants suitable for the purpose of theinvention are Coco N-hydroxyethyl-N,N-dimethyl ammonium salts andcholine ester. Other conventional useful surfactants are listed instandard texts.

Additional detergent components

The detergent compositions of the invention may also contain additionaldetergent components. The precise nature of these additional components,and levels of incorporation thereof will depend on the physical form ofthe composition, and the nature of the cleaning operation for which itis to be used.

The compositions of the invention may for example, be formulated as handand machine laundry detergent compositions, including laundry additivecompositions and compositions suitable for use in the pretreatment ofstained fabrics and machine dishwashing compositions.

When formulated as compositions suitable for use in a machine washingmethod, eg: machine laundry and machine dishwashing methods, thecompositions of the invention preferably contain one or more additionaldetergent components selected from bleach activators and preformedperacids, bleaching agents and mixtures thereof. When preformed peracidsare used, they may be selected from amidoperacid, diperacid and mixturesthereof.

Bleach activators

If present, the amount of bleach activators will typically be from 0.1%to 60%, more typically from 0.5% to 40% of the detergent composition.These activators contains one or more N- or O-acyl groups and can beselected from a wide range of classes.

Various nonlimiting examples of activators are disclosed in U.S. Pat.No. 4,915,854, issued Apr. 10, 1990 to Mao et al, and U.S. Pat. No.4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetylethylene diamine (TAED) activators are typical, and mixtures thereof canalso be used. Also included as bleach activators are the benzoyloxybenzene sulfonate as disclosed in, for example, EP-A-0341947 andcationic derivatives of the benzoyl oxybenzene sulphonates. See alsoU.S. 4,634,551 for other typical bleaches and activators useful herein.

A useful class of bleach activators is the amido suds suppressorprecursors of the invention, which may also function as an activator.These activators can additionally be used with other activators such asdescribed herein (NOBS, TAED, benzoxazin activators, acyl lactamactivators and cationic activators and mixtures thereof)

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR9##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR10## wherein R⁶ is H or an alkyl, aryl,alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms.Highly preferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof. See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8,1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

Another class of preferred bleach activators include the cationic bleachactivators, derived from the valerolactam and acyl caprolactamcompounds, of formula: ##STR11## wherein x is 0 or 1, substituents R, R'and R" are each C₁ -C₁₀ alkyl or C₂ -C₄ hydroxy alkyl groups, or (C_(y)H_(2y))O!_(n) -R'" wherein y=2-4, n=1-20 and R'" is a C₁ -C₄ alkyl groupor hydrogen and X is an anion.

Bleaching agents

The detergent compositions herein may optionally contain bleachingagents. When present, bleaching agents will typically be at levels offrom 1% to 30%, more typically from 5% to 20%, of the detergentcomposition, especially for fabric laundering.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents. Alkalimetal perborate bleaches, e.g., sodium perborate (e.g., mono- ortetra-hydrate) can be used herein.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent of "percarbonate" bleaches, sodium pyrophosphateperoxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulphatebleach (e.g., OXONE, manufactured commercially by DuPont) can also beused.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from 500 micrometers to 1,000micrometers, not more than 10% by weight of said particles being smallerthan 200 micrometers and not more than 10% by weight of said particlesbeing larger than 1,250 micrometers. Optionally, the percarbonate can becoated with silicate, borate or water-soluble surfactants. Percarbonateis available from various commercial sources such as FMC, Solvay andTokai Denka.

Mixtures of bleaching agents can also be used.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patentapplication Ser. No. 740,446, Burns et al, filed Jun. 3, 1985, EuropeanPatent Application 0,133,354, Banks et al, published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid and nonyl amido peroxy adipic acid as described in U.S. Pat. No.4,634,551, issued Jan. 6, 1987 to Burns et al.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from 0.025% to 1.25%, byweight, of such bleaches, especially sulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalysed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. No. 5,246,621, U.S. Pat. No. 5,244,594; U.S. Pat. No. 5,194,416;U.S. Pat. No. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1,549,272A1, 544,440A2, and 544,490A1; Preferred examples of thesecatalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF6)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄ -(u-O)(u-OAc)₂ -(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃, Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃ (PF₆), and mixturesthereof. Other metal-based bleach catalysts include those disclosed inU.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following U.S. Pat. Nos. 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from 0.1 ppm to 700ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species inthe laundry liquor.

ADJUNCT INGREDIENTS

The compositions herein can optionally include one or more otherdetergent adjunct materials or other materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or to modify the aesthetics of the detergent composition (e.g.,perfumes, colorants, dyes, etc.). The following are illustrativeexamples of such adjunct materials.

Builders

Detergent builders can optionally be included in the compositions hereinto assist in controlling mineral hardness. Inorganic as well as organicbuilders can be used. Builders are typically used in fabric launderingcompositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least 1% builder. Liquidformulations typically comprise from 5% to 50%, more typically 5% to30%, by weight, of detergent builder. Granular formulations typicallycomprise from 10% to 80%, more typically from 15% to 50% by weight, ofthe detergent builder. Lower or higher levels of builder, however, arenot meant to be excluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called "weak" builders(as compared with phosphates) such as citrate, or in the so-called"underbuilt" situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂ : Na₂ O ratio in the range 1.6:1 to3.2:1 and layered silicates, such as the layered sodium silicatesdescribed in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P.Rieck. NaSKS-6 is the trademark for a crystalline layered silicatemarketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlikezeolite builders, the Na SKS-6 silicate builder does not containaluminum. NaSKS-6 has the delta-Na₂ Si₂ O₅ morphology form of layeredsilicate. It can be prepared by methods such as those described inGerman DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferredlayered silicate for use herein, but other such layered silicates, suchas those having the general formula NaMSi_(x) O_(2x+1) yH₂ O wherein Mis sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and yis a number from 0 to 20, preferably 0 can be used herein. Various otherlayered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, asthe alpha, beta and gamma forms. As noted above, the delta-Na₂ Si₂ O₅(NaSKS-6 form) is most preferred for use herein. Other silicates mayalso be useful such as for example magnesium silicate, which can serveas a crispening agent in granular formulations, as a stabilising agentfor oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    Na.sub.z  (AlO.sub.2).sub.z (SiO.sub.2).sub.y !.xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to 0.5, and x is an integer from 15 to 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

    Na.sub.12  (AlO.sub.2).sub.12 (SiO.sub.2).sub.12 !.xH.sub.2 O

wherein x is from 20 to 30, especially 27. This material is known asZeolite A. Dehydrated zeolites (x=0-10) may also be used herein.Preferably, the aluminosilicate has a particle size of 0.1-10 microns indiameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate" refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralised salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also"TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅ -C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Chelating Agents

The detergent compositions herein may also optionally contain one ormore iron and/or manganese chelating agents. Such chelating agents canbe selected from the group amino carboxylates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturestherein, all as hereinafter defined. Without intending to be bound bytheory, it is believed that the benefit of these materials is due inpart to their exceptional ability to remove iron and manganese ions fromwashing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the S,S! isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from 0.1% to10% by weight of the detergent compositions herein. More preferably, ifutilized, the chelating agents will comprise from 0.1% to 3.0% by weightof such compositions.

Enzymes

Enzymes can be included in the formulations herein for a wide variety offabric laundering purposes, including removal of protein-based,carbohydrate-based, or triglyceride-based stains, for example, and forthe prevention of refugee dye transfer, and for fabric restoration. Theenzymes to be incorporated include proteases, amylases, lipases,cellulases, and peroxidases, as well as mixtures thereof. Other types ofenzymes may also be included. They may be of any suitable origin, suchas vegetable, animal, bacterial, fungal and yeast origin. However, theirchoice is governed by several factors such as pH-activity and/orstability optima, thermostability, stability versus active detergents,builders and so on. In this respect bacterial or fungal enzymes arepreferred, such as bacterial amylases and proteases, and fungalcellulases.

Enzymes are normally incorporated at levels sufficient to provide up to5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme pergram of the composition. Stated otherwise, the compositions herein willtypically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation. Protease enzymes are usually present insuch commercial preparations at levels sufficient to provide from 0.005to 0.1 Anson units (AU) of activity per gram of composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S under the registered trade name ESPERASE. The preparationof this enzyme and analogous enzymes is described in British PatentSpecification No. 1,243,784 of Novo. Proteolytic enzymes suitable forremoving protein-based stains that are commercially available includethose sold under the tradenames ALCALASE and SAVINASE by Novo IndustriesA/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (TheNetherlands). Other proteases include Protease A (see European PatentApplication 130,756, published Jan. 9, 1985) and Protease B (seeEuropean Patent Application Serial No. 87303761.8, filed Apr. 28, 1987,and European Patent Application 130,756, Bott et al, published Jan. 9,1985).

Amylases include, for example, α-amylases described in British PatentSpecification No. 1,296,839 (Novo), RAPIDASE, InternationalBio-Synthetics, Inc. and TERMAMYL, Novo Industries. FUNGAMYL (Novo) isespecially useful.

The cellulase usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, issued Mar. 6, 1984, which discloses fungal cellulaseproduced from Humicola insolens and Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk(Dolabella Auricula Solander). suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) isespecially useful.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Pat. No. 1,372,034. See alsolipases in Japanese Patent Application 53,20487, laid open to publicinspection on Feb. 24, 1978. This lipase is available from AmanoPharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P"Amano," hereinafter referred to as "Amano-P." Other commercial lipasesinclude Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacterviscosum var. lipolyticum NRRLB 3673, commercially available from ToyoJozo Co., Tagata, Japan; and further Chromobacter viscosum lipases fromU.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, andlipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived fromHumicola lanuginosa and commercially available from Novo (see also EPO341,947) is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulphate, hydrogen peroxide, etc. They areused for "solution bleaching," i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813, published Oct. 19, 1989,by O. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978,and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985, both.Enzyme materials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use indetergents can be stabilised by various techniques. Enzyme stabilisationtechniques are disclosed and exemplified in U.S. Pat. No. 3,600,319,issued Aug. 17, 1971 to Gedge, et al, and European Patent ApplicationPublication No. 0 199 405, Application No. 86200586.5, published Oct.29, 1986, Venegas. Enzyme stabilisation systems are also described, forexample, in U.S. Pat. No. 3,519,570.

Clay Soil Removal/Anti-redeposition Agents

The compositions of the present invention can also optionally containwater-soluble ethoxylated amines having clay soil removal andantiredeposition properties. Granular detergent compositions whichcontain these compounds typically contain from 0.01% to 10.0% by weightof the water-soluble ethoxylates amines; liquid detergent compositionstypically contain 0.01% to 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. Another type of preferred antiredeposition agentincludes the carboxy methyl cellulose (CMC) materials. These materialsare well known in the art.

Polymeric Dispersing Agents

Polymeric dispersing agents can advantageously be utilized at levelsfrom 0.1% to 7%, by weight, in the compositions herein, especially inthe presence of zeolite and/or layered silicate builders. Suitablepolymeric dispersing agents include polymeric polycarboxylates andpolyethylene glycols, although others known in the art can also be used.It is believed, though it is not intended to be limited by theory, thatpolymeric dispersing agents enhance overall detergent builderperformance, when used in combination with other builders (includinglower molecular weight polycarboxylates) by crystal growth inhibition,particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerising orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerised to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerised acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom 2,000 to 10,000, more preferably from 4,000 to 7,000 and mostpreferably from 4,000 to 5,000. Water-soluble salts of such acrylic acidpolymers can include, for example, the alkali metal, ammonium andsubstituted ammonium salts. Soluble polymers of this type are knownmaterials. Use of polyacrylates of this type in detergent compositionshas been disclosed, for example, in Diehl, U.S. Pat. No. 3,308,067,issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from 2,000 to 100,000, more preferably from 5,000 to75,000, most preferably from 7,000 to 65,000. The ratio of acrylate tomaleate segments in such copolymers will generally range from 30:1 to1:1, more preferably from 10:1 to 2:1. Water-soluble salts of suchacrylic acid/maleic acid copolymers can include, for example, the alkalimetal, ammonium and substituted ammonium salts. Soluble acrylate/maleatecopolymers of this type are known materials which are described inEuropean Patent Application No. 66915, published Dec. 15, 1982, as wellas in EP 193,360, published Sep. 3, 1986, which also describes suchpolymers comprising hydroxypropylacrylate. Still other useful dispersingagents include the maleic/acrylic/vinyl alcohol terpolymers. Suchmaterials are also disclosed in EP 193,360, including, for example, the45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from 500 to 100,000, preferably from1,000 to 50,000, more preferably from 1,500 to 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of 10,000.

Polymeric Soil Release Agent

Any polymeric soil release agent known to those skilled in the art canoptionally be employed in the compositions and processes of thisinvention. Polymeric soil release agents are characterised by havingboth hydrophilic segments, to hydrophilize the surface of hydrophobicfibers, such as polyester and nylon, and hydrophobic segments, todeposit upon hydrophobic fibers and remain adhered thereto throughcompletion of washing and rinsing cycles and, thus, serve as an anchorfor the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

The polymeric soil release agents useful herein especially include thosesoil release agents having: (a) one or more nonionic hydrophilecomponents consisting essentially of (i) polyoxyethylene segments with adegree of polymerisation of at least 2, or (ii) oxypropylene orpolyoxypropylene segments with a degree of polymerisation of from 2 to10, wherein said hydrophile segment does not encompass any oxypropyleneunit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethyleneand from 1 to 30 oxypropylene units wherein said mixture contains asufficient amount of oxyethylene units such that the hydrophilecomponent has hydrophilicity great enough to increase the hydrophilicityof conventional polyester synthetic fiber surfaces upon deposit of thesoil release agent on such surface, said hydrophile segments preferablycomprising at least 25% oxyethylene units and more preferably,especially for such components having 20 to 30 oxypropylene units, atleast 50% oxyethylene units; or (b) one or more hydrophobe componentscomprising (i) C₃ oxyalkylene terephthalate segments, wherein, if saidhydrophobe components also comprise oxyethylene terephthalate, the ratioof oxyethylene terephthalate:C₃ oxyalkylene terephthalate units is 2:1or lower, (ii) C₄ -C₆ alkylene or oxy C₄ -C₆ alkylene segments, ormixtures therein, (iii) poly (vinyl ester) segments, preferablypolyvinyl acetate), having a degree of polymerisation of at least 2, or(iv) C₁ -C₄ alkyl ether or C₄ hydroxyalkyl ether substituents, ormixtures therein, wherein said substituents are present in the form ofC₁ -C₄ alkyl ether or C₄ hydroxyalkyl ether cellulose derivatives, ormixtures therein, and such cellulose derivatives are amphiphilic,whereby they have a sufficient level of C₁ -C₄ alkyl ether and/or C₄hydroxyalkyl ether units to deposit upon conventional polyestersynthetic fiber surfaces and retain a sufficient level of hydroxyls,once adhered to such conventional synthetic fiber surface, to increasefiber surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerisation of from 200, although higher levels can be used,preferably from 3 to 150, more preferably from 6 to 100. Suitable oxy C₄-C₆ alkylene hydrophobe segments include, but are not limited to,end-caps of polymeric soil release agents such as MO₃ S(CH₂)_(n) OCH₂CH₂ O--, where M is sodium and n is an integer from 4-6, as disclosed inU.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosic polymers,copolymeric blocks of ethylene terephthalate or propylene terephthalatewith polyethylene oxide or polypropylene oxide terephthalate, and thelike. Such agents are commercially available and include hydroxyethersof cellulose such as METHOCEL (Dow). Cellulosic soil release agents foruse herein also include those selected from the group C₁ -C₄ alkyl andC₄ hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093, issued Dec. 28,1976 to Nicol, et al.

Soil release agents characterised by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.Commercially available soil release agents of this kind include theSOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (WestGermany).

One type of preferred soil release agent is a copolymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentis in the range of from 25,000 to 55,000. See U.S. Pat. No. 3,959,230 toHays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issuedJul. 8, 1975.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units contains 10-15% by weightof ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON 5126 (from Dupont)and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct.27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are described fully in U.S. Pat. No. 4,968,451, issuedNov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitablepolymeric soil release agents include the terephthalate polyesters ofU.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, theanionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issuedJan. 26, 1988 to Gosselink, and the block polyester oligomeric compoundsof U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil releaseagents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado etal, which discloses anionic, especially sulfoarolyl, end-cappedterephthalate esters.

If utilized, soil release agents will generally comprise from 0.01% to10.0%, by weight, of the detergent compositions herein, typically from0.1% to 5%, preferably from 0.2% to 3.0%.

Still another preferred soil release agent is an oligomer with repeatunits of terephthaloyl units, sulfoisoterephthaloyl units,oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form thebackbone of the oligomer and are preferably terminated with modifiedisethionate end-caps. A particularly preferred soil release agent ofthis type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units,oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from 1.7 to1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)-ethanesulphonate. Said soil release agent alsocomprises from 0.5% to 20%, by weight of the oligomer, of acrystalline-reducing stabiliser, preferably selected from the groupxylene sulfonate, cumene sulfonate, toluene sulfonate, and mixturesthereof.

Dye Transfer Inhibiting Agents

The compositions of the present invention may also include one or morematerials effective for inhibiting the transfer of dyes from one fabricto another during the cleaning process. Generally, such dye transferinhibiting agents include polyvinyl pyrrolidone polymers, polyamineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,manganese phthalocyanine, peroxidases, and mixtures thereof. If used,these agents typically comprise from 0.01% to 10% by weight of thecomposition, preferably from 0.01% to 5%, and more preferably from 0.05%to 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R--A_(x)--P; wherein P is a polymerizable unit to which an N--O group can beattached or the N--O group can form part of the polymerizable unit orthe N--O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N═; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN--O group can be attached or the N--O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N--O group can be represented by the following general structures:##STR12## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N--O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa<10, preferably pKa<7, more preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1: 1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerisation. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as "PVPVI") are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113."Modern Methods of Polymer Characterization", the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone ("PVP") having an average molecular weight of from5,000 to 400,000, preferably from 5,000 to 200,000, and more preferablyfrom 5,000 to 50,000. PVP's are known to persons skilled in thedetergent field; see, for example, EP-A-262,897 and EP-A-256,696,incorporated herein by reference. Compositions containing PVP can alsocontain polyethylene glycol ("PEG") having an average molecular weightfrom 500 to 100,000, preferably from 1,000 to 10,000. Preferably, theratio of PEG to PVP on a ppm basis delivered in wash solutions is from2:1 to 50: 1, and more preferably from 3:1 to 10:1.

The detergent compositions herein may also optionally contain from0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from 0.01% to 1%by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula: ##STR13## wherein R₁ is selectedfrom anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selectedfrom N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, morphilino,chloro and amino; and M is a salt-forming cation such as sodium orpotassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is 4,4',-bis(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino!-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightenerspecies is commercially marketed under the tradename Tinopal-UNPA-GX byCiba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilicoptical brightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is4,4'-bis(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino!2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is 4,4'-bis(4-anilino-6-morphilino-s-triazine-2-ylmorphilino-s-triazine-2-yl)amino!2,2'-stilbenedisulfonic acid, sodiumsalt. This particular brightener species is commercially marketed underthe tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory, it is believed that such brighteners work this waybecause they have high affinity for fabrics in the wash solution andtherefore deposit relatively quick on these fabrics. The extent to whichbrighteners deposit on fabrics in the wash solution can be defined by aparameter called the "exhaustion coefficient". The exhaustioncoefficient is in general as the ratio of a) the brightener materialdeposited on fabric to b) the initial brightener concentration in thewash liquor. Brighteners with relatively high exhaustion coefficientsare the most suitable for inhibiting dye transfer in the context of thepresent invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric "brightness" benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Brightener

Any optical brighteners or other brightening or whitening agents knownin the art can be incorporated at levels typically from 0.05% to 1.2%,by weight, into the detergent compositions herein. Commercial opticalbrighteners which may be useful in the present invention can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents. Examplesof such brighteners are disclosed in "The Production and Application ofFluorescent Brightening Agents", M. Zahradnik, Published by John Wiley &Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, available fromHilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H-naptho1,2-d!triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes;4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific examples ofthese brighteners include 4-methyl-7-diethyl- amino coumarin;1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines;2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho 1,2-d!oxazole; and2-(stilben-4-yl)-2H-naphtho 1,2-d!triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton. Anionic brighteners arepreferred herein.

Fabric Softeners

Various through-the-wash fabric softeners, especially the impalpablesmectite clays of U.S. Pat. No. 4,062,647, Storm and Nirschl, issuedDec. 13, 1977, as well as other softener clays known in the art, canoptionally be used typically at levels of from 0.5% to 10% by weight inthe present compositions to provide fabric softener benefitsconcurrently with fabric cleaning. Clay softeners can be used incombination with amine and cationic softeners as disclosed, for example,in U.S. Pat. No. 4,375,416, Crisp et al, Mar. 1, 1983 and U.S. Pat. No.4,291,071, Harris et al, issued Sep. 22, 1981.

Other Ingredients

A wide variety of other ingredients useful in detergent compositions canbe included in the compositions herein, including other activeingredients, carriers, hydrotropes, processing aids, dyes or pigments,solvents for liquid formulations, solid fillers for bar compositions,etc.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5 X theweight of silica. The resulting powder is dispersed with stirring insilicone oil (various silicone oil viscosities in the range of500-12,500 can be used). The resulting silicone oil dispersion isemulsified or otherwise added to the final detergent matrix. By thismeans, ingredients such as the aforementioned enzymes, bleaches, bleachactivators, bleach catalysts, photoactivators, dyes, fluorescers, fabricconditioners and hydrolyzable surfactants can be "protected" for use indetergents, including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactants, but polyols such asthose containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups(e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol)can also be used. The compositions may contain from 5% to 90%, typically10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between 6.5 and 11, preferably between 7.5 and 10.5.

Liquid dishwashing product formulations preferably have a pH between 6.8and 9.0. Laundry products are typically at pH 9-11. Techniques forcontrolling pH at recommended usage levels include the use of buffers,alkalis, acids, etc., and are well known to those skilled in the art.

The detergent composition of the present invention is effective in softand hard water and can be used in a well built formulation, wherein thebuilder content is at least 125% by weight of the formulation, as wellas in a low built formulation, wherein the builder content is less than15% by weight of the formulation.

The invention is illustrated in the following non limiting examples, inwhich all percentages are on a weight basis unless otherwise stated.

In the detergent compositions, the abbreviated component identificationshave the following meanings:

LAS : Sodium linear C₁₂ alkyl benzene sulphonate

XYAS : Sodium C_(1X) -C_(1Y) alkyl sulphate

APG : Alkyl polyglycoside surfactant of formula C₁₂ -(glycosyl)x, wherex is 1.5,

24EY : A C₁₂₋₁₄ predominantly linear primary alcohol condensed with anaverage of Y moles of ethylene oxide

45EY : A C₁₄ -C₁₅ predominantly linear primary alcohol condensed with anaverage of Y moles of ethylene oxide

XYEZS : C_(1X) -C_(1Y) sodium alkyl sulphate condensed with an averageof Z moles of ethylene oxide per mole

NaSKS-6: Crystalline layered silicate of formula δ- Na₂ Si₂ O₅

Carbonate : Anhydrous sodium carbonate

MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weightabout 80,000

Zeolite A : Hydrated Sodium Aluminosilicate of formula Na₁₂ (AlO₂SiO₂)₁₂.27H₂ O having a primary particle size in the range from 1 to 10micrometers

Citrate : Tri-sodium citrate dihydrate

Citric : Citric Acid

Percarbonate : Anhydrous sodium percarbonate bleach of empirical formula2Na₂ CO₃.3H₂ O₂ coated with a mixed salt of formula Na₂ SO₄.n.Na₂ CO₃where n is 0.29 and where the weight ratio of percarbonate to mixed saltis 39:1

TAED : Tetraacetyl ethylene diamine

Protease : Proteolytic enzyme sold under the tradename Savinase by NovoIndustries A/S (approx 2% enzyme activity).

Lipase : Lipolytic enzyme sold under the tradename Lipolase by NovoIndustries A/S (approx 2% enzyme activity)

Cellulase : Cellulosic enzyme sold under the tradename Carezyme by NovoIndustries A/S.

Endo A: Tradename of a cellulosic enzyme sold by Novo Industries A/S

PVNO : Polyvinyl pyridine N-oxide polymer of molecular weight 10,000

MgSO4: Anhydrous Magnesium Sulphate

SRP : modified anionic polyester Soil Release Polymer

CMC : Sodium carboxymethyl cellulose

EDDS: Ethylenediamine-N,N'-disuccinic acid, S,S! isomer in the form ofthe sodium salt.

silicone 25% paraffin wax Mpt 50° C., 17% hydrophobic silica, 58%paraffin oil.

Suds Testing Method

110 g of the detergent formulations described herein after are taken andadded to a Miele 698 washing machine containing 1.5 kg of clean, newterry towel ballast. The products are tested at 90° C., main wash cycle,using soft water (3° Clark).

The % suds is measured and calculated using the following expression:##EQU1## 4 replicates of each product are completed.

EXAMPLE 1

i)-detergent compositions

The following compositions were prepared and tested for sudsing.Composition A formed wash liquor in accordance with the prior art whilecomposition 1 formed wash liquor in accordance with the invention andcomposition 2 embodiment of the invention show the suds suppressioneffect of differing types of amidoacid and amidoperacid.

The suds suppressor in composition 1 was a 50:50 blend of 6-octanamidocaproyl oxy benzene sulphonate and 6-decanamido caproyl oxy benzenesulphonate, while the suds suppressor in composition 2 was a 50:50 blendof 6-octanamido caproic acid and 6-decanamido caproic acid.

    ______________________________________                                                      A       1       2                                               ______________________________________                                        TAED            5         --      --                                          6-Octanamido/   --        5       --                                          6 Decanamido                                                                  Caproyl Oxy Benzene                                                           Sulphonate (50:50 blend)                                                      6-Octanamido/   --        --      5                                           6 Decanamido                                                                  Caproic Acid (50:50 blend)                                                    C45AS           10        10      10                                          C25AE3S         2         2       2                                           C24E5           3         3       3                                           N-Methyl Glucamide                                                                            3         3       3                                           Zeolite A       17        17      17                                          SKS-6           12        12      12                                          Citric          3         3       3                                           MA/AA           5         5       5                                           CMC             0.4       0.4     0.4                                         PEG             0.5       0.5     0.5                                         Savinase        2.4       2.4     2.4                                         Lipolase        0.2       0.2     0.2                                         Cellulase       0.2       0.2     0.2                                         Endo A          0.2       0.2     0.2                                         SRP             0.4       0.4     0.4                                         PVNO            0.02      0.02    0.02                                        Carbonate       6         6       6                                           Zinc Phthalocyanine                                                                           20 ppm    20 ppm  20 ppm                                      sulphonate                                                                    Silicone        0.4       0.4     0.4                                         Percarbonate    20        20      20                                          Water minors and miscellaneous to balance                                     ______________________________________                                    

ii)-suds results

The above compositions are evaluated for sudsing with the suds methoddescribed herein before in medium hard water (12° Clark).

    ______________________________________                                                    A         1     2                                                 ______________________________________                                        % suds (30 mns)                                                                             85          28    6                                             ______________________________________                                    

The amidoacid alone gives a a very effective suds suppressing action atthe foaming from the surfactant system.

EXAMPLE 2

i)-detergent compositions

The following compositions were prepared and tested for sudsing.Compositions A, B, C formed wash liquors in accordance with the priorart while composition 1, 2, 3, 4 formed wash liquors in accordance withthe invention show the suds suppression effect of differing levels ofamidoacid and amidoperacid.

The suds suppressor in compositions 1-4 was a 50:50 blend of6-octanamido caproyl oxy benzene sulphonate and 6-decanamido caproyl oxybenzene sulphonate.

    ______________________________________                                               A    B       C      1     2    3     4                                 ______________________________________                                        LAS      10     --      --   10    --   --    --                              C45AS    --     10      10   --    10   10    10                              Silicone 0.3    0.3     0.3  0.3   --   0.3   0.3                             TAED     5      5       --   --    --   --    3                               6-Octanamido                                                                           --     --      --   5     5    5     3                               6 Decanamido                                                                  Caproyl Oxy                                                                   Benzene                                                                       Sulphonate                                                                    (50:50 blend)                                                                 C45E7    4      4       4    4     4    4     4                               Zeolite A                                                                              18     18      18   18    18   18    18                              SKS-6    8      8       8    8     8    8     8                               Citric   4      4       4    4     4    4     4                               MA/AA    4      4       4    4     4    4     4                               SRP      0.3    0.3     0.3  0.3   0.3  0.3   0.3                             CMC      0.3    0.3     0.3  0.3   0.3  0.3   0.3                             EDDS     0.4    0.4     0.4  0.4   0.4  0.4   0.4                             MgSO4    0.4    0.4     0.4  0.4   0.4  0.4   0.4                             Percarbonate                                                                           18     18      18   18    18   18    18                              Carbonate                                                                              4.5    4.5     4.5  4.5   4.5  4.5   4.5                             Savinase 1.2    1.2     1.2  1.2   1.2  1.2   1.2                             Lipolase 0.4    0.4     0.4  0.4   0.4  0.4   0.4                             Cellulase                                                                              0.1    0.1     0.1  0.1   0.1  0.1   0.1                             Water minors and miscellaneous to balance                                     ______________________________________                                    

ii)-suds results

    ______________________________________                                                  A    B      C      1    2    3    4                                 ______________________________________                                        % suds at 30 minutes                                                                      70     100    100  65   60   12   25                              ______________________________________                                    

From the suds test above, it is seen that LAS is a lower foamingsurfactant than coco AS.

After 30 mns of stressed suds testing, the blend is perhydrolized in itsperacid form, said peracid giving the acid. The mixture, of amidoacidand amidoperacid suds suppressor, obtained reduces the foaming of LASand AS. A better reduction is seen with the foaming of the ASsurfactant.

EXAMPLE 3

i)-detergent compositions

The following compositions were prepared and tested for sudsing andcleaning. Compositions A and B formed wash liquors in accordance withthe prior art while compositions 1, 2, 3 formed wash liquors inaccordance with the invention show the suds suppression effect ofdiffering levels of amidoacid and amidoperacid.

The suds suppressor in compositions 1-3 was a 50:50 blend of6-octanamido caproyl oxy benzene sulphonate and 6-decanamido caproyl oxybenzene sulphonate.

    ______________________________________                                               A     B        1        2      3                                       ______________________________________                                        TAED     --      6        --     4      --                                    6-Octanamido/                                                                          --      --       5      3      3                                     6 Decanamido                                                                  Caproyl Oxy                                                                   Benzene                                                                       Sulphonate                                                                    (50:50 blend)                                                                 Benzoyl  --      --       --     --     4                                     Caprolactam                                                                   C45AS    10      10       10     10     10                                    C25AE3S  2       2        2      2      2                                     C24E5    3       3        3      3      3                                     N-Methyl 3       3        3      3      3                                     Glucamide                                                                     Zeolite A                                                                              17      17       17     17     17                                    SKS-6    12      12       12     12     12                                    Citric   3       3        3      3      3                                     MA/AA    5       5        5      5      5                                     CMC      0.4     0.4      0.4    0.4    0.4                                   PEG      0.5     0.5      0.5    0.5    0.5                                   Savinase 2.4     2.4      2.4    2.4    2.4                                   Lipolase 0.2     0.2      0.2    0.2    0.2                                   Cellulase                                                                              0.2     0.2      0.2    0.2    0.2                                   Endo A   0.2     0.2      0.2    0.2    0.2                                   SRP      0.4     0.4      0.4    0.4    0.4                                   PVNO     0.02    0.02     0.02   0.02   0.02                                  Carbonate                                                                              6       6        6      6      6                                     Zinc     20 ppm  20 ppm   20 ppm 20 ppm 20 ppm                                Phthalocyanin                                                                 e sulphonate                                                                  Silicone 0.4     0.4      0.4    0.4    0.4                                   Percarbonate                                                                           20      20       20     20     20                                    Water minors and miscellaneous to balance                                     ______________________________________                                    

ii)-suds results

The above compositions are evaluated for sudsing with the suds methoddescribed herein before and for performance on a range of hydrophobicand body soils by using a launderometer at 40° C. with hard water (12°Clark)

    ______________________________________                                                  A      B      1        2    3                                       ______________________________________                                        % suds (30 mns)                                                                           100      100    15     30   22                                    Performance                                                                   (psu vs A)                                                                    lipstick    0        +0.5   +4.0s  +3.0s                                                                              +3.5s                                 shoe polish 0        +0.6   +4.0s  +3.0s                                                                              +3.6s                                 tea         0        +3.0   +1.5   +2.8 +3.3                                  coffee      0        +2.8   +1.3   +2.5 +3.1                                  ______________________________________                                    

The mixture obtained of amidoacid and amidoperacid gives a veryeffective suds suppressing action at the foaming from the surfactantsystem and also provides effective cleaning performance on hydrophobicsoils like lipstick and polish.

Furthermore, when the detergent composition of the invention isformulated with additional precursor like TAED or benzoyl caprolactam,the suds suppression properties and performance on hydrophobic stains aswell as the performance on hydrophilic stains like tea and coffee areretained.

EXAMPLE 4

i)-detergent compositions

The following compositions were prepared and tested for sudsing.Compositions A and B formed wash liquors in accordance with the priorart while composition 1, 2, 3 formed wash liquors in accordance with theinvention show the suds suppression effect of differing levels ofamidoacid and amidoperacid.

The suds suppressor in compositions 1-3 was a 50:50 blend of6-octanamido caproyl oxy benzene sulphonate and 6-decanamido caproyl oxybenzene sulphonate.

    ______________________________________                                               A      B        1        2      3                                      ______________________________________                                        TAED     --       6        --     4      --                                   6-Octanamido/                                                                          --       --       5      3      3                                    6 Decanamido                                                                  Caproyl Oxy                                                                   Benzene                                                                       Sulphonate                                                                    (50:50 blend)                                                                 Benzoyl  --       --       --     --     4                                    Caprolactam                                                                   C45AS    5        5        5      5      5                                    C12-C14 alkyl                                                                          5        5        5      5      5                                    (N-hydroxy                                                                    ethyl-N,N-                                                                    dimethyl                                                                      ammonium                                                                      bromide)                                                                      C25AE3S  2        2        2      2      2                                    C24E7    3        3        3      3      3                                    N-Methyl 3        3        3      3      3                                    Glucamide                                                                     Zeolite A                                                                              17       17       17     17     17                                   SKS-6    12       12       12     12     12                                   Citric   3        3        3      3      3                                    MA/AA    5        5        5      5      5                                    CMC      0.4      0.4      0.4    0.4    0.4                                  PEG      0.5      0.5      0.5    0.5    0.5                                  Savinase 2.4      2.4      2.4    2.4    2.4                                  Lipolase 0.2      0.2      0.2    0.2    0.2                                  Carezyme 0.2      0.2      0.2    0.2    0.2                                  Endo A   0.2      0.2      0.2    0.2    0.2                                  SRP      0.4      0.4      0.4    0.4    0.4                                  PVNO     0.02     0.02     0.02   0.02   0.02                                 Carbonate                                                                              6        6        6      6      6                                    Zinc     20 ppm   20 ppm   20 ppm 20 ppm 20 ppm                               Phthalocyanin                                                                 e sulphonate                                                                  Silicone 0.4      0.4      0.4    0.4    0.4                                  Percarbonate                                                                           20       20       20     20     20                                   Water minors and miscellaneous to balance                                     ______________________________________                                    

ii)-Suds results

The above compositions are evaluated for sudsing with the suds methoddescribed herein before in medium hard water (12° Clark).

    ______________________________________                                                  A        B     1        2   3                                       ______________________________________                                        % suds (30 mns)                                                                           100        95    35     45  41                                    ______________________________________                                    

The mixture of amidoacid and amidoperacid suds suppressors obtained fromthe amido acid precursor is very effective at suppressing the suds of amixed AS/cationic surfactant system.

EXAMPLE 5

i)-Detergent compositions

The following compositions were prepared and tested for sudsing.Composition A formed wash liquor in accordance with the prior art whilecomposition 1 and 2 formed wash liquors in accordance with the inventionshow the suds suppression effect of differing levels/types of amidoacidand amidoperacid.

The suds suppressor in composition 1 was 6-nonanoyl caproyl oxy benzenesulphonate, while the suds suppressor in composition 2 was nonyl amidoperoxy adipic acid.

    ______________________________________                                                  A         1       2                                                 ______________________________________                                        TAED        4.5         --      --                                            6-Nonanoyl  --          3       --                                            Caproyl Oxy                                                                   Benzene                                                                       Sulphonate                                                                    (Mwt 287)                                                                     Nonyl Amido --          --      1.9                                           Peroxy Adipic                                                                 Acid (Mwt 287)                                                                C45AS       10          10      10                                            C25AE3S     2           2       2                                             C24E5       3           3       3                                             N-Methyl    3           3       3                                             Glucamide                                                                     Zeolite A   17          17      17                                            SKS-6       12          12      12                                            Citric      3           3       3                                             MA/AA       5           5       5                                             CMC         0.4         0.4     0.4                                           PEG         0.5         0.5     0.5                                           Savinase    2.4         2.4     2.4                                           Lipolase    0.2         0.2     0.2                                           Carezyme    0.2         0.2     0.2                                           Endo A      0.2         0.2     0.2                                           SRP         0.4         0.4     0.4                                           PVNO        0.02        0.02    0.02                                          Carbonate   6           6       6                                             Zinc        20 ppm      20 ppm  20 ppm                                        Phthalocyanine                                                                sulphonate                                                                    Silicone    0.4         0.4     0.4                                           Percarbonate                                                                              20          20      20                                            Water minors and miscellaneous to balance                                     ______________________________________                                    

ii)-Suds results

The above compositions are evaluated for sudsing with the suds methoddescribed herein before in soft water (3° Clark) and in hard water (18°Clark).

    ______________________________________                                        % suds (20 mns)                                                                             A           1     2                                             ______________________________________                                        Soft water    80          35    49                                            Hard water    81          31    43                                            ______________________________________                                    

The mixture of amidoacid and amidoacid suds suppressor obtained from theamido acid precursor is an effective suds suppression agent of highfoaming surfactants in hard water, as well as in soft water. The mixtureof said suds suppressor agent also gives better suds suppression resultsthan the nonyl amido peroxy adipic acid.

EXAMPLE 6

i)-detergent compositions

The following compositions were prepared and tested for sudsing andcleaning. Composition A formed wash liquor in accordance with the priorart while compositions 1, 2, 3, 4, 5 formed wash liquors in accordancewith the invention show the suds suppression effect of differinglevels/types of amidoacid and amidoperacid.

The suds suppressor in compositions 1-4 was a 50:50 blend of6-octanamido caproyl oxy benzene sulphonate and 6-decanamido caproyl oxybenzene sulphonate, while the suds suppressor in composition 5 was6-decanamido caproyl oxy benzene sulphonate.

    ______________________________________                                               A     1       2       3     4     5                                    ______________________________________                                        Percarbonate                                                                           17      --      17    8     25    17                                 Additional                                                                             --      12      --    6     --    --                                 Carbonate                                                                     6-Octanamido/                                                                          --      3       3     3     3     --                                 6 Decanamido                                                                  Caproyl Oxy                                                                   Benzene                                                                       Sulphonate                                                                    (50:50 blend)                                                                 6 Decanamido                                                                           --      --      --    --    --    3                                  Caproyl Oxy                                                                   Benzene                                                                       Sulphonate                                                                    C45AS    10      10      10    10    10    10                                 C25AE3S  2       2       2     2     2     2                                  C24E5    3       3       3     3     3     3                                  N-Methyl 3       3       3     3     3     3                                  Glucamide                                                                     Zeolite A                                                                              17      17      17    17    17    17                                 SKS-6    12      12      12    12    12    12                                 Citric   3       3       3     3     3     3                                  MA/AA    5       5       5     5     5     5                                  CMC      0.4     0.4     0.4   0.4   0.4   0.4                                PEG      0.5     0.5     0.5   0.5   0.5   0.5                                Savinase 2.4     2.4     2.4   2.4   2.4   2.4                                Lipolase 0.2     0.2     0.2   0.2   0.2   0.2                                Carezyme 0.2     0.2     0.2   0.2   0.2   0.2                                Endo A   0.2     0.2     0.2   0.2   0.2   0.2                                SRP      0.4     0.4     0.4   0.4   0.4   0.4                                PVNO     0.02    0.02    0.02  0.02  0.02  0.02                               Carbonate                                                                              6       6       6     6     6     6                                  Zinc     20 ppm  20 ppm  20 ppm                                                                              20 ppm                                                                              20 ppm                                                                              20 ppm                             Phthalocyanine                                                                sulphonate                                                                    Silicone 0.4     0.4     0.4   0.4   0.4   0.4                                Water minors and miscellaneous to balance                                     ______________________________________                                    

ii)-suds and performance results

The above compositions are evaluated for sudsing with the suds methoddescribed herein before in medium hard water (12° Clark).

    ______________________________________                                                  A       1       2     3     4     5                                 ______________________________________                                        % suds (25 mns)                                                                         100     30      44    60    6511  35                                Performance                                                                   (40° C.)                                                               Lipstick   0      +1.6    +3.8  +3.5  +3.6  +4.0                              Polish     0      +1.4    +3.6  +3.2  +3.6  +4.0                              ______________________________________                                    

Both the amidoacid or the mixture of amidoacid and amidoperacid obtainedfrom the amidoacid precursor act as a suds suppressor agent and giveeffective cleaning performance on hydrophobic soils like lipstick andpolish.

From the results above, it is seen that the percarbonate:amido acidprecursor ratio may be varied without detracting significantly from itsperformance or suds suppressing properties.

EXAMPLE 7

i)-detergent compositions

The following compositions were prepared and tested for sudsing.Compositions 1, 2, 3, 4, 5, 6, 7 formed wash liquors in accordance withthe invention show the suds suppression effect of amidoacid andamidoperacid.

The suds suppressor in compositions 1-7 was a 50:50 blend of6-octanamido caproyl oxy benzene sulphonate and 6-decanamido caproyl oxybenzene sulphonate.

    ______________________________________                                               1    2       3      4     5    6     7                                 ______________________________________                                        6-octanamido/                                                                          3      3       3    3     3    3     3                               6 Decanamido                                                                  Caproyl Oxy                                                                   Benzene                                                                       Sulphonate                                                                    (50:50 blend)                                                                 Benzoyl  4      4       4    4     4    4     4                               Caprolactam                                                                   Percarbonate                                                                           17     17      17   17    17   17    17                              C45 AS   12     6       --   9     12   14.3  10                              C38 AS   3      3       --   2     3    3.7   3.7                             C25 AES  3      1.5     3    2     3    --    --                              C24 E3   5      --      --   --    --   5     5                               Palm N-Methyl                                                                          4      9       --   4     9    4     4                               Glucamide                                                                     APG      --     --      9    5     --   --    --                              Oleyl    --     7.5     15   5     --   --    --                              Sarcosinate                                                                   Amine Oxide                                                                            --     --      --   --    --   --    4                               Zeolite A                                                                              5      5       5    5     5    5     5                               SKS-6    7      7       7    7     7    7     7                               Citric Acid/                                                                           3      3       3    3     3    3     3                               Citrate                                                                       Carbonate                                                                              9      9       9    9     9    9     9                               MA/AA    5      5       5    5     5    5     5                               EDDS     0.25   0.25    0.25 0.25  0.25 0.25  0.25                            Silicone 0.6    0.6     0.6  0.6   0.6  0.6   0.6                             Water minors, enzymes and miscellaneous to balance                            ______________________________________                                    

The mixture of amidoacid and amidoperacid obtained from the amidoacidprecursor acts as a very effective suds suppressing agent with variousmixed surfactant systems and also gives a good bleaching activity onhydrophobic soils.

I claim:
 1. An aqueous wash liquor comprising:(a) a detersive surfactantcomprising a C₁₀ -C₂₀ alkyl sulphate; (b) an ingredient selected fromthe group consisting of sulfonated zinc phthalocyanines, sulfonatedaluminum phthalocyanines and mixtures thereof; and (c) a suds suppressorcompound of the formula: ##STR14## wherein said suds suppressor isformed from a suds suppressor precursor of formula: ##STR15## wherein R₁is an allyl, aryl or alkaryl group containing from 1 to 14 carbon atoms,R₂ is an alkaline, arylene or alkarylene group containing from 1 to 14carbon atoms, and R₅ is H or an alkyl, aryl, or alkaryl group containingfrom 1 to 10 carbon atoms and L is a leaving group.
 2. An aqueous washliquor according to claim 1, further containing additional sudssuppressor agents selected from the group consisting of silicone,lecithin, and defoaming mixtures containing paraffin wax and bis-amide.3. An aqueous wash liquor according to claim 1, wherein L is selectedfrom the group consisting of ##STR16## and mixtures thereof, wherein R₁is as defined in claim 1, R₃ is an alkyl chain containing from about 1to about 8 carbon atoms, R4 is H or R3, and Y is H or a solubilisinggroup.
 4. An aqueous wash liquor according to claim 3, wherein L has thegeneral formula: ##STR17##
 5. An aqueous wash liquor according to claim1, wherein said suds suppressor precursor is at a level of at least0.1%.
 6. A method of suppressing sudsing, comprising the step of addingto a detergent composition a component selected from the groupconsisting of: ##STR18## and mixtures thereof; wherein R₁ is an alkyl,aryl or alkaryl group containing from 1 to 14 carbon atoms, R₂ is analkaline, arylene or alkarylene group containing from 1 to 14 carbonatoms, R₅ is H or an alkyl, aryl, or alkaryl group containing from 1 to10 carbon atoms and L is a leaving groups;wherein the detergentcomposition comprises a C₁₀ -C₂₀ alkyl sulphate and an ingredientselected from the group consisting of sulfonated zinc phthalocyanines,sulfonated aluminum phthalocyanines and mixtures thereof.
 7. A detergentcomposition according to claim 6, wherein L is selected from the groupconsisting of: ##STR19## and mixtures thereof, wherein R₁ is an alkyl,aryl or alkaryl group containing from about 1 to about 14 carbon atoms,R₃ is an alkyl chain containing from about 1 to about 8 carbon atoms, R₄is H or R₃, and Y is H or a solubilizing group.